Esters of aryl-aliphatic alcohols

ABSTRACT

Esters of aryl-aliphatic alcohols, useful as antiviral agents and insecticides, are prepared by reacting an arylalkyl or arylalkenyl iodide with an alkali metal salt of the appropriate acid.

United States Patent [1 Diana et al.

{45] June 24, 1975 ESTERS 0F ARYL-ALIPHATIC ALCOHOLS [75] Inventors: Guy D. Diana, Stephentown;

William B. Hinshaw, .lr., Sand Lake,

both of NY.

[73] Assignee: Sterling Drug Inc., New York, NY.

[22] Filed: Jan. 17, 1973 [2]] Appl. No.: 324,543

[56] References Cited FOREIGN PATENTS OR APPLICATIONS l,0l9,348 2/1966 United Kingdom 260/29] R OTHER PUBLICATIONS Closson et al., Tetrahedron Letters, N0. 48, pages 6015-6020 (l966) Ansell et al., J. Chem. Soc. [956, pages 1238 to 1242.

Colonge et al., Bull. Soc. Chim. France, 1963, pages 1799 to 1802.

Primary Examiner-John D. Randolph Attorney, Agent, or FirmThomas L. Johnson; B. Woodrow Wyatt [57] ABSTRACT Esters of aryI-aliphatic alcohols, useful as antiviral agents and insecticides, are prepared by reacting an arylalkyl or arylalkenyl iodide with an alkali metal salt of the appropriate acid.

7 Claims, N0 Drawings ESTERS OF ARYL-ALIPHATIC ALCOHOLS ORGANIC COMPOUNDS AND THEIR PREPARATION This invention relates to esters of aryl-aliphatic alco- 5 hols and to the preparation thereof.

The compounds of the invention are of the structural formula 3 R C-O- CH CH Y-Ar wherein Y is selected from the group consisting of:

R is hydrogen or lower-alkyl of l to 4 carbon atoms;

and

Ar is phenyl substituted by 3,4-methyienedioxy or one or two monovalent substituents selected from the group consisting of lower-alkoxy of 1 to 4 carbon atoms, carbo-lower-alkoxy of 2 to 4 carbon atoms, halogen, trifluoromethyl and trifluoromethoxy.

The carbon chains of R, R and Ar substituents can be straight or branched, although primary or secondary alkyl moieties are preferred.

When R is a saturated or mono-olefinic hydrocarbon moiety having from i to 10 carbon atoms, it includes alkyl, alkenyl, cycloalkyl, cycloalkenyl, and combinations thereof such as alkylcycloalkyl, alkylcycloalkenyl, alkenylcycloalkyl, and the like.

When two monovalent substituents are present on the phenyl ring of Ar, they can be the same or different.

Intermediates for the compounds of the invention are prepared as described in the following reaction sequences.

Reaction Seguence A C CH AI S "3 OHC-Ar E II III 2 Ar A 2 1) P131 2) ZnBr /CH CH AI Br 2 on; ca 2\CH2 Reaction Seguence A-Cominued CH c CH Ar I 2 CH 2 R VI CH 3H CH A 2\ 2\ BI CH CH CH CH CH\ Ar 1 CH 0H,; 2 on! VIa In the foregoing Reaction Sequence A, a 30 lithium bromide to replace the hydroxy group by bromine, which product is then treated with zinc bromide to effect ring opening to form an arylalkenyl bromide of formula V. The latter with a metallic iodide is converted to the corresponding iodide of formula VI. If a 35 compound with a saturated alkylene chain is desired the unsaturated bromide of formula V is hydrogenated in the presence of palladium or platinum oxide catalyst to produce a saturated bromide of formula Va, which is in turn converted to the corresponding iodide Vla.

Reaction Seguence B CH Ar as 2x or w VII FBI- 2) ZnBr I I CH /C\\CH/CH CH In Reaction Sequence B the arylvinyl l-R- cyclopropyl ketone of formula III is treated with an al kali metal borohydride, preferably sodium borohydride to reduce the carbonyl group but not the olefmic linkage and provide an arylvinyl l-Rcyclopropyl carbinol of formula VII. By procedures analogous to those shown in Reaction Sequence A, the carbinol of formula VII is treated with phosphorus tribromide in the presence of a metal bromide and then with zinc bromide to give a diunsaturated aralkyl bromide of formula VIII. The latter is then converted to the corresponding iodide (IX).

The compounds of formula I, where Y is C(R)==CHCH CI-I CH(R)CH CI-l CH or C(R)=CHCH=CH-, can be prepared from the intermediates described above according to the following method: 0

I-CH CH -YAr VI, VIa, IX

RCOCHQCHQYAI' An arylalkyl iodide of formula Vla or an arylalkenyl iodide of formula VI or IX is reacted with an alkali metal salt of an acid R'COOM where M is an alkali metal and R, Y and Ar have the meanings given hereinabove. The reaction takes place in an inert organic solvent at a temperature between about 30C. and IO0C.

The compounds of formula I where Y is more of a variety of viruses, including rhino-2, equine rhino, para-influenza and respiratory syncitial virus at minimal growth inhibitory concentrations (mic) ranging from about 0.5 to about 50 micrograms per milliliter. The mic values were determined by standard serial dilution procedures.

The compounds of the invention have also been found to possess pesticidal activity against arthropod species, as indicated by tests under simulated field conditions in a greenhouse against one or more of the following pest species: yellow mealworm pupae, dock beetle larvae, cabbage looper larvae, yellow fever mosquito larvae, rhodnius prolixus nymph, dock beetle eggs and salt marsh caterpillar eggs.

The structures of the compounds of the invention were established by the modes of synthesis, by elementary analysis, and by infrared and nuclear magnetic resonance spectral determinations.

A further aspect of the invention relates to compositions for combatting arthropods by hindering the maturation thereof which comprise an effective amount of at least one compound of formula I in admixture with a suitable carrier or diluent, and to the method of combatting arthropods at any stage of their development by contacting them with said compositions.

The compositions of the invention are effective against insects at any stage of their development short of the final adult form, i.e. at the egg, larval or pupal stages. The compounds can be formulated in conventional manner as solutions, emulsions, suspensions, dusts and aerosol sprays. The pesticide compositions of the invention can contain adjuvants found normally in such preparations, including water and/or organic solvents such as acetone, dimethylformamide, sesame oil, petroleum oils, and the like. Emulsifying and surface active agents may also be added. Dust formulations can contain talc, diatomaceous earth, kaolin, bentonite, calcium carbonate, wood, flour, cork, carbon, and the like. The aerosol sprays contain propellants such as dichlorodifluoromethane. The compounds of this invention can be employed as the sole pesticide component or they can be used in admixture with other compounds having similar utility. While the concentration of active ingredient can vary within rather wide limits, ordinarily the pesticide will comprise not more than about 10%, and preferably about I% by weight of the composition.

A still further aspect of the invention relates to compositions for combatting viruses which comprise an an tivirally effective amount of at least one compound of formula I in admixture with a suitable carrier or diluent, and to the method of combatting viruses by contacting the locus of said viruses with said compositions.

The antiviral compositions are formulated by preparing a dilute solution or suspension in an organic or aqueous-organic medium, for example ethyl alcohol. acetone, dimethylsulfoxide, and the like; and are applied to the locus to be disinfected by conventional means such as spraying, swabbing or immersing. Alternatively, the compounds can be formulated as ointments or creams by incorporating them in conventional ointment or cream bases, such as alkylpolyether alcohols, cetyl alcohol, stearyl alcohol and the like; as jellies by incorporating them in conventional jelly bases such as glycerin and tragacanth; or as aerosol sprays or foams.

The following examples will further illustrate the invention.

PREPARATION OF INTERMEDIATES A. 2-Arylvinyl cyclopropyl ketones ([ll) A1. 2-(3,4-Methylenedioxyphenyl)vinyl l-ethylcyclopropyl ketone llll; Ar is 3,4-methylenedioxyphenyl, R is C H A mixture of 33.6 g. (0.3 mole) of l-ethylcyclopropyl methyl ketone and 45 g. (0.3 mole) of piperonal in 2l ml. of ethanol was stirred at room temperature, and 21 ml. of 20% aqueous sodium hydroxide was added dropwise over a period of 30-45 minutes. The mixture was warmed at 4060C. for 3 hours with stirring. The solution was then cooled to 0l0C., 0.2 ml. of glacial acetic acid added, and the mixture was extracted with ether. The ether extracts were concentrated, and the residue dissolved in 200 ml. of 95% ethanol, which solution when cooled caused separation of a solid product. The latter was recrystallized from 150 ml. of methanol to give 39 g. of 2-(3,4-methylenedioxyphenyl )vinyl l-ethylcyclopropyl ketone, m.p. 62'64C.

A2. 2-(3,4Methylenedioxyphenyl)vinyl cyclopropyl ketone (Ill; Ar is 3,4-methylenedioxyphenyl, R is H] was prepared from 8.4 g. of cyclopropyl methyl ketone and g. of piperonal according to the procedure described above in Preparation Al, affording 21.5 g., m.p. 85-87C. when recrystallized from ethanol.

A3. 2-(3,4-Methylenedioxyphenyl)vinyl l-methylcyclopropyl ketone [[1]; Ar is 3,4-methylenedioxyphenyl, R is CH was prepared from 25.6 g. of l-methylcyclopropyl methyl ketone and 39.3 g. of piperonal according to the procedure described above in Preparation Al, affording 29.5 g. of crystalline product.

A4. 2-(3,4-Dimethoxyphenyl)vinyl l-ethylcyclopropyl ketone [ll]; Ar is 3,4(CH O) C H R is C H was prepared from 22.4 g. of l-ethylcyclopropyl methyl ketone and 33.2 g. of veratraldehyde according to the procedure described above in Preparation A1, affording 20.3 g., b.p. l56l58C. (0.02 mm).

A5. 2-(4-Methoxypheny1)vinyl cyclopropyl ketone [1"; Ar is 4-CH OC H R is H] was prepared from 84.l g. of cyclopropyl methyl ketone and 136 g. of pmethoxybenzaldehyde according to the procedure described above in Preparation Al, affording 173.5 g., m.p. 70-72C. when recrystallized from ethanol.

A6. 2-(4-Chlorophenyl)vinyl cyclopropyl ketone (Ill; Ar is 4ClC H R is H] was prepared from 25.2 g. of cyclopropyl methyl ketone and 42 g. of chlorobenzaldehyde according to the procedure (i scribed above in Preparation Al, affording 31 g., m.p. 6365C. when recrystallized from ethanol.

A7. 2-(4-Carboxyphenyl)vinyl l-ethylcyclopropyl ketone [I|l; Ar is 4HO CC H R is C H was prepared from 67.2 g. of l-ethylcyclopropyl methyl ketone and g. of p-carboxybenzaldehyde according to the procedure described above in Preparation Al, affording 40 g., m.p. l83.5-184.5C. when recrystallized from acetonitrile and then repeatedly from isopropyl alcohol.

By following the procedure of Preparation Al above, l-isopropylcyclopropyl methyl ketone or l-butylcyclopropyl methyl ketone can be caused to react with piperonal to give 2-(3,4-methylenedioxyphenyl)vinyl l-isopropylcyclopropyl ketone [1"; Ar is 3,4- methylenedioxyphenyl, R is (CH CH], or 2-(3,4- methylenedioxyphenyl)vinyl l-butylcyclopropyl ketone [II]; Ar is 3,4-methylenedioxyphenyl, R is cu cmcmcun, respectively.

By following the procedure of Preparation Al above, cyclopropyl methyl ketone can be caused to react with 3,4-dichlorobenzaldehyde, 2,4-dichlorobenzaldehyde, 4-bromobenzaldehyde, 4-fluorobenzalclehyde, 4- trifluoromethoxybenzaldehyde or 4-trifluoromethylbenzaldehyde to give, respectively:

2-(3,4-dichlorophenyl)vinyl cyclopropyl ketone [ll];

2-(2,4-dichlorophenyl)vinyl cyclopropyl ketone [ll];

Ar is 2,4-Cl C H R is H], 2-(4-bromophenyl)vinyl cyclopropyl ketone [1"; Ar

is 4-BrC H R is H], 2-(4-fluorophenyl)vinyl cyclopropyl ketone [[il', Ar

is 4FC,,H,, R is H], 2-(4-trifluoromethoxyphenyl)vinyl cyclopropyl ketone [llI; Ar is 4-F COC H R is H], or 2-(4-trifluoromethylphenyl)vinyl cyclopropyl ketone (Ill; Ar is 4F;,CC H R is H].

B. 2-Arylethyl cyclopropyl carbinols (1V) and Z-arylvinyl cyclopropyl carbinols (Vll) Bl. 2-(3 ,4-Methylenedioxyphenyl)ethyl l-ethylcyclopropyl carbinol [lV; Ar is 3,4- methylenedioxyphenyl, R is C H A suspension of 15 g. of lithium aluminum hydride in about 500 ml. of tetrahydrofuran was heated at reflux while a solution of 60 g. of 2-(3,4-methylenedioxyphenyl)vinyl l-ethylcyclopropyl ketone (Preparation Al in ml. of tetrahydrofuran was added dropwise over a period of 2-3 hours. The reaction mixture was heated at reflux for 2 hours, cooled, and then water was added very cautiously. Excess anhydrous sodium sulfate was added, the mixture filtered, and the filter cake washed several times with chloroform. The combined filtrate and washings were evaporated to dryness to give 53 g. of an oil consisting of 2-(3,4-methylenedioxyphenyl)ethyl l-ethylcyclopropyl carbinol.

B2. 2-(3,4-Methylenedioxyphenyl)ethyl cyclopropyl carbinol [IV; Ar is 3,4-methylenedioxyphenyl, R is H] was prepared from 18.4 g. of 2-(3,4-methylenedioxyphenyl)vinyl cyclopropyl ketone (Preparation A2) and 3.1 g. of lithium aluminum hydride according to the procedure described above in Preparation Bl, affording 11.5 g., b.p. ll6l22C. (0.005 mm.), m.p. 6 .-65C. when recrystallized from ether.

.33. 2-(3,4-Methylenedioxyphenyl)ethyl l-methylcysp xl carbinol (IV; Ar is 3,4- '.iemylenedioxyphenyl, R is CH was prepared from 23.4 g. of 2-(3,4-methylenedioxyphenyl)vinyl l-methylcyclopropyl ketone (Preparation A3) and 3.88 g. of lithium aluminum hydride according to the procedure described above in Preparation B1, affording 18.8 g., b.p. l20-130C. (0.003 mm.).

B4. 2-(3,4-Dimeth0xyphenyl)ethyl l-ethylcyclopropyl carbinol [[V; Ar is 3,4(CH;,O) C H R is C H was prepared from g. of 2-(3,4-dimethoxyphenyl)vinyl l-ethylcyclopropyl ketone (Preparation A4) and 2.2 g. of lithium aluminum hydride according to the procedure described above in Preparation B1, affording 10 g., b.p. l48l50C. (0.01 mm.).

B5. 2-(Methoxyphenyl)ethyl cyclopropyl carbinol [[V; Ar is 4CH OC H R is H] was prepared from 50 g. of 2-(4-methoxyphenyl)vinyl cyclopropyl ketone (Preparation A5) and 9.7 g. of lithium aluminum hydride according to the procedure described above in Preparation Bl affording 42 g., b.p. 116l 17C. (005 mm.).

B6. 2-(4-Chlorophenyl)ethyl cyclopropyl carbinol [1V; AR is 4ClC H4,R is H] was prepared from 31 g of 2-(4-chlorophenyl)vinyl cyclopropyl ketone (Preparation A6) and 5.87 g. of lithium aluminum hydride according to the procedure described above in Preparation Bl, affording 23.8 g., b.p. l05106C. (0.1 mm.).

B7. 2-(4-Carb0xyphenyl)vinyl l-ethylcyclopropyl carbinol [V]l; Ar is 4HO CC H R is C H To a stirred suspension of 34.0 g. of 2-(4-carboxyphenyl)vinyl l-ethylcyclopropyl ketone (Preparation A7) in 500 ml. of ice water was slowly added 1 1 g. of sodium borohydride over a 1 hour period. The mixture was stirred for about 16 hours and then cautiously acidified with ice-cold concentrated hydrochloric acid. The solid material was collected by filtration and dissolved in ether. The ether solution was dried over anhydrous magnesium sulfate and concentrated to give 33.2 g. of 2-(4-carboxyphenyl)vinyl l-ethylcyclopropyl carbinol, m.p. l30-131C. when recrystallized from toluene.

B8. 2-(4-Carboxyphenyl)ethyl l-ethylcyclopropyl carbinol [[V; Ar is 4HO CC.;H R is C H A solution of 29 g. of 2-(4-carboxyphenyl)vinyl l-ethylcyclopropyl carbinol (Preparation B7) in 200 ml. of ethanol was hydrogenated in the presence of l g. of palladiumon-carbon catalyst. There was thus obtained 28 g. of 2-(4-carboxyphenyl)ethyl l-ethylcyclopropyl carbinol, colorless crystals, m.p. l l6l 17.5C.

B9. 2-(3,4-Methylenedioxyphenyl)vinyl l-ethylcyclopropyl carbinol [Vll; Ar is 3,4- methylenedioxyphenyl, R is C H To a cold solution of 5 g. of 2-(3,4-methylenedioxyphenyl)vinyl l-ethylcyclopropyl ketone (Preparation A1 in 50 ml. of methanol was added in portions 1.56 g. of sodium borohydride. The mixture was stirred at room temperature for 2 hours, then diluted with water and extracted with ether. The ether extracts were dried and concentrated to give 3.6 g. of 2-(3,4-methylenedioxyphenyl)vinyl l-ethylcyclopropyl carbinol as a colorless oil.

By replacing the 2-(3,4-methylenedioxyphenyl)vinyl l-ethylcyclopropyl ketone in Preparation B1 above by a molar equivalent amount of 2-(3,4-methylenedioxyphenyl)vinyl l-isopropylcycloprpyl ketone, 2-(3,4- methylenedioxyphenyl)vinyl l-butylcyclopropyl ketone, 2-(3,4-dichlorophenyl)vinyl cyclopropy ketone, 2-(2,4-dichlorophenyl)vinyl cyclopropyl ketone, 2-(4- bromophenyhvinyl cyclopropyl ketone, 2-(4- fluorophenyl )vinyl cyclopropyl ketone, 2-( 4- trifluoromethoxyphenyl)vinyl cyclopropyl ketone or 2(4-trifluoromethylphenyl)vinyl cyclopropyl ketone there can be obtained, respectively:

{1V; Ar is 2,4Cl C 1-l R is H], 2-(4-bromophenyl)ethyl cyclopropyl carbinol [[V;

Ar is 4BrC H,, R is H], 2-(4-fluorophenyl)ethyl cyclopropyl carbinol [[V; Ar

is 4FC H R is H], 2-(4-trifluoromethoxyphenyl)ethyl cyclopropyl carbinol [1V; Ar is 4F COC H R is H], or 2-(4-trifluoromethylphenyl)ethyl cyclopropyl carbinol [[V; Ar is 4F CC 1-h, R is H].

C. Arylalkenyl bromides (V, V111) and arylalkyl bromides (Va) Cl. 3-Ethyl-6-(3,4-methylenedioxyphenyl)-3-hexenyl bromide [V; Ar is 3,4-methylenedioxyphenyl, R is C ll To a solution of 26.4 g. (0.106 mole) of 2-(3,4- methylenedioxyphenyl)ethyl l-ethylcyclopropyl carbinol in 250 ml. of ether, cooled to 30C. under nitrogen, was added 18 ml. of collidine. Lithium bromide (26 g., 0.3 mole) was then added, the mixture cooled to -50C. and 25 g. (0.09 mole) of phosphorus tribromide was added dropwise. The reaction mixture was stirred at 50C. for 10 minutes, allowed to warm to 0C. over a 3 hour period and stirred at 0C. for 3 hours. Collidine (30 ml.) was added, followed by 10 ml. of water. The reaction mixture was partitioned between water and ether, the ether layer washed with water and sodium chloride solution, and dried over anhydrous magnesium sulfate. The ether solution was concentrated to give an oily product used directly in the following reaction.

The latter product was dissolved in about 200 ml. of anhydrous ether and added in a fine stream to a stirred mixture of 27 g. of zinc bromide in 200 ml..of ether held at 30 to 35C. The mixture was stirred, then allowed to warm to 0C. during 2 hours, held there for 30 minutes, and then allowed to warm to room temperature over a 3 hour period and stirred for 2 hours longer. The reaction mixture was partitioned between ether and aqueous sodium chloride. The ether layer was washed three times with 500 ml. of water, then with sodium chloride solution, dried over anhydrous magnesium sulfate and concentrated to remove the solvent. The residue was redissolved in ether, washed with dilute aqueous sodium bicarbonate and with sodium chloride solution, and evaporated to give 23 g. of 3- ethyl-6(3,4-methylenedioxyphenyl)-3-hexenyl bromide as a straw-colored oil.

C2. 6-(3,4-Methylenedioxyphenyl)-3-hexenyl bromide [V; Ar is 3,4-methylenedioxyphenyl, R is H] was prepared from 1 1.5 g. of 2-(3,4-methylenedioxyphenyl)ethyl cyclopropyl carbinol (Preparation B2), 12 g. of phosphorus tribromide, 10 g. of lithium bromide and 12.7 g. of zinc bromide according to the procedure given above in Preparation C1, affording 12.5 g. of product as an oilv C3. 3-Methyl-6-( 3 ,4-methylenedioxyphenyl )-3- hexenyl bromide l; Ar is 3,4-methylenedioxyphenyl, R is CH was prepared from 17.6 g. of 2-(3,4-

methylenedioxyphenyl)ethyl l -methylcyclopropylcarbinol (Preparation B3), 20.3 g. of phosphorus tribromide, 18.5 g. of lithium bromide and 21 g. of zinc bromide according to the procedure given above in Preparation C1, affording 19 g. of product as an oil.

C4. 3-Ethyl-6-(3,4-dimethoxyphenyl)-3-hexeny1 bromide [V; Ar is 3,4(CH O) C H R is C H ]was prepared from 16 g. of 2-(3,4-dimethoxyphenyl)ethyl l-ethylcyclopropyl carbinol (preparation B4), 16.8 g. of phosphorous tribromide, 16.8 g. of lithium bromide and 17.6 g. of zinc bromide according to the procedure given above in Preparation C1. The product was used directly in the succeeding step (Preparation D4) without isolation.

C5. 6-(4-Methoxyphenyl-3-hexenyl bromide [V; Ar is 4-CH OC H R is H] was prepared from 38.2 g. of 2-(4-methoxyphenyl)ethyl cyclopropyl carbinol (Preparation B5 42.5 g. of phosphorus tribromide, 35 g. of

lithium bromide and 40 g. of zinc bromide according to the procedure given above in Preparation C 1 affording 48 g. of product as an oil.

C6. 6-(4-Chlorophenyl)-3-hexenyl bromide (V; Ar is 4ClC H,, R is H] was prepared from 21 g. of 2-(4- chlorophenyl)ethyl cyclopropyl carbinol (Preparation B6), 23 g. ofphosphorus tribromide, 18.85 g. oflithium bromide and 22.5 g. of zinc bromide according to the procedure given above in Preparation C1, affording 25.5 g. of product as an oil.

C7. 3-Ethyl-6-(4-carbomethoxyphenyl)-3-hexenyl bromide [V; Ar is 4CH O CC,;H R is C H A mixture of 21.3 g. of 2-(4-carboxyphenyl)vinyl l-ethylcyclopropyl carbinol (Preparation B7) and 500 ml. of methanol saturated with hydrogen chloride at 0C. was stirred for 1 hour at 0C. and then allowed to come to room temperature with stirring until the solution was complete. The reaction mixture was concentrated to dryness, the residue taken up in chloroform and washed with water and sodium bicarbonate solution, dried over anhydrous magnesium sulfate and concentrated to give 24.4 g. of a light yellow oil. The latter product was dissolved in a small quantity of ether and added to a solution of 700 g. of zinc bromide in 4 liters of anhydrous ether. The reaction mixture was stirred for hours. then washed with water, dried over anhydrous magnesium sulfate and the solvent evaporated, affording 17.5 g. of 3-ethyl-6-(4- carbomethoxyphenyl)-3-hexenylbromide as a light yellow oil.

C8. 3-Ethyl-6-(3.4-methylenedioxyphenyl)-3,5- hexadienyl bromide VIII; Ar is 3,4- methylenedioxyphenyl, R is C H was prepared from 3.6 g. of 2-(3,4methylenedioxyphenyl)vinyl l-ethylcyclopropyl carbinol (Preparation B9), 3.5 g. of phosphorus tribromide, 4.5 g. of lithium bromide and 3.5 g. of phosphorus tribromide. 4.5 g. of lithium bromide and 3.5 g. of zinc bromide according to the procedure given above in Preparation C1, affording 2 g. of product as an oil.

C9. 6-(4-methoxyphenyl)hexyl bromide [Va; Ar is 4CH OC H R is H]. A mixture of 18.6 g. of 6-(4-methoxypheny1)-3-hexenyl bromide (Preparation C5) and 0.21 g. of platinum oxide catalyst in 200 m1. of isopropyl alcohol was hydrogenated until 1 mole equivalent of hydrogen had been absorbed. The product was isolated and distilled to give 12.8 g. of 6-(4-methoxyphenyl)hexyl bromide, bp. l26l28C. (0.04 mm).

(10. 6-t4-Chloroohenvllhexvl bromide lVa: Ar is 4ClC H R is H] was prepared by hydrogenation of 25.2 g. of 6-(4-chlorophenyl)-3-hexenyl bromide (Preparation C6) according to the procedure described above in Preparation C9, affording 17 g., b.p. 1l0111C. (0.02 mm.).

By replacing the 2-(3.4-methylenedioxyphenyl)ethyl l-ethylcyclopropy carbinol in Preparation Clby a molar equivalent amount of 2(3,4-methylenedioxyphenyl)ethyl l-isopropylcyclopropyl carbinol, 2-(3,4- methylenedioxyphenyl)ethyl l-butylcyclopropyl carbin01, 2-(3,4-dichloropheny1)ethyl cyclopropyl carbinol, 2-(2,4-dichlorophenyl)ethyl cyclopropyl carbinol, 2-(4-bromophenyl1ethyl cyclopropyl carbinol, 2(4- fluorophenyhethyl cyclopropyl carbinol, 2-(4- trifluorornethoxyphenyl)ethyl cyclopropyl carbinol or 2-(4-trifluoromethylphenyl)ethyl cyclopropyl carbinol there can be obtained, respectively:

3-isopropyl-6-(3,4-methylenedioxyphenyl)-3- hexenyl bromide V; Ar is methylenedioxyphenyl, R is (CH CH], 3-butyl-6-(3,4-methylenedioxyphenyl)-3-hexenyl bromide [V; Ar is 3,4-methylenedioxyphenyl, R is CH Cl-l Cl-l Ci-l l, 6-(3,4-dichlorophenyl)-3-hexeny1 bromide [V; Ar is 3,4-CI C H R is H], 6-(2,4-dichlorophenyl)-3-hexenyl bromide [V; Ar is 2,4C1 C H R is H], 6-(4-bromophenyl)-3-hexenyl bromide [V; Ar is 4BrC.,I-I R is H], 6-(4-fluoropheny1)-3-hexenyl bromide [V; Ar is 4-FC H,, R is H], 6-(4-trifluoromethoxyphenyl)-3-hexeny1 [V; Ar is 4F COC H R is H], or 6-(4-trifluoromethylphenyl)-3-hexenyl bromide [V;

Ar is 4F CC H R is H]. The latter products can be hydrogenated according to the procedure of Preparation C9 to give, respectively:

3-isopropyl-6-(3,4-methylenedioxyphenyl)hexyl bromide [Va; Ar is 3,4-methylenedioxyphenyl, R is (CH3)2CHL 3-butyl-6-(3,4-methy1enedioxyphenyl )hexyl bromide [Va; Ar is 3,4-methylenedioxyphenyl, R is C H C H C H C H 6-(3,4-dichlorophenyl)hexy1 bromide [Va; Ar is 3.4Cl C I-1 R is H],

6-(2,4-dichlorophenyl)hexyl bromide [Va; Ar is 2,4Cl-,C H R is H],

6-(4-bromophenyl)hexyl bromide [Va; Ar is 4- BrC H R is H],

6-(4-fluorophenyl)hexyl PC 11 R is H],

6-(4-trifluoromethoxyphenyl)hexyl bromide [Va; Ar

is 4F;,COC H R is H], or

6-(4-trifluoromethylphenyl)hexyl bromide [Va; Ar is 4F CC H R is H].

D. Aryalkenyl iodides (V1, IX) and arylalkyl iodides (Vla) D1. 3-Ethyl-6-( 3,4-methylenedioxyphenyl) 3- hexenyl iodide [Vl; Ar is 3,4-methylenedioxyphenyl, R is C H A mixture of 23 g. of 3-ethyl-6-(3,4- methylenedioxyphenyl)-3-hexenyl bromide (Preparation Cl and 30 g. ofpowdered potassium iodide in 250 ml. of dimethylformamide was stirred for about 16 hours. The reaction mixture was concentrated to remove the solvent and the residue partitioned between cyclohexane and water. The cyclohexane layer was separated, dried over anhydrous magnesium sulfate bromide bromide [Va; Ar is 4- and evaporated to give 33.0 g. of 3-ethyl-6-(3,4- methylencdioxyphenyl)-3-hexenyl iodide as a light yellow oil.

D2. 6-(3,4-Methylenedioxyphenyl)-3-hexenyl iodide [V|; Ar is 3,4-methylenedioxyphenyl, R is H] was prepared from 12.9 g. of 6-(3,4-methylenedioxypheny1)-3- hexenyl bromide (Preparation C2) and 7 g. of sodium iodide in 120 ml. of acetone, refluxed for 3 hours, atfording 12.5 g. of product as an oil.

D3. hexenyl iodide [V1, Ar is 3,4-methylenedioxyphenyl, R is CH was prepared from 19.0 g. of 3-methyl-6'(3,4- methylenedioxyphenyl)-3-hexenyl bromide (Preparation C3) and 10.5 g. of sodium iodide in 125 ml. of acetone, to give 21 g. of product as a yellow oil.

D4. 3-Ethyl-6-(3,4-dimethoxyphenyl)-3-hexenyl iodide [V]; Ar is 3,4(CH O) C H R is C H was prepared from 13.8 g. of 3-ethyl-6-(3,4-dimethoxyphenyl)-3-hexenyl bromide (Preparation C4) and 9 g. of sodium iodide in 120 ml. of acetone, to give 15 g. of product as an oil.

D5. 6-(4-Methoxyphenyl)-3-hexenyl iodide [Vl; Ar is 4-CH OC H,, R is H] was prepared from 24 g. of 6-(4-methoxyphenyl)-3-hexenyl bromide (Preparation C5) and 14.75 g. of sodium iodide in 475 ml. of 2- butanone, to give 28.5 g. of product as an oil.

D6. 6-(4-Methoxyphenyl)hexyl iodide [Vla; Ar is 4CH OC H R is H] was prepared from 16.3 g. of 6-(4-methoxyphenyl)hexyl bromide (Preparation C9) and 9.93 g. of sodium iodide in 325 m1. of Z-butanone, to give 19.3 g. of product as a pale yellow oil.

D7. 6-(4-Chlorophenyl)hexyl iodide [Vla,' Ar is 4CIC,,H R is H] was prepared from 17 g. of 6-(4- chlorophenyl)hexyl bromide (Preparation C) and 10.2 g. of sodium iodide in 325 ml. of acetone, to give 21 g. of product as an oil.

D8. 3-Ethyl-6-(4-carbomethoxyphenyl)-3-hexenyl iodide (V1; Ar is 4CH O CC H R is C H was pre pared from 17.5 g. of 3-ethyl-6-(4carbomethoxyphenyl)-3-hexenyl bromide (Preparation C7) and 17.5 g. of sodium iodide in 200 ml. of acetone, to give 14 g. of product as an oil.

D9. 3-Ethyl-6-(3,4-methylenedioxyphenyl)-3,5- hexadienyl iodide [IX; Ar is 3,4- methylenedioxyphenyl, R is C H was prepared from 10 g. of 3-ethyl-6-(3,4-methylenedioxyphenyl)-3,5- hexadienyl bromide (Preparation C8) and 6 g. of so dium iodide in 120 ml. of acetone, to give 10.5 g. of product as an oil.

By similar procedures 3-isopropyl-6-(3,4- methylenedioxyphenyl)hexyl bromide, 3-butyl-6-(3,4-

methylenedioxyphenyl)hexyl bromide, 6-(3,4- dichlorophenyl)hexyl bromide, 6-(2,4- dichlorophenyl )hexyl bromide, 6-(4- 3-butyl-6-(3,4-methylenedioxyphenyl)hexyl iodide [Vla; Ar is 3,4-methylenedioxyphenyl, R is CH CH CH CH 6-(3,4-dichlorophenyl)hexyl iodide [Vla; Ar is 3,4Cl C H R is H], 6-(2,4dichlorophenyl)hexyl iodide (Via; Ar is 3-Methyl-6-(3,4-methylenedioxyphenyl)-3- 10 6-(4-bromophenyl)hexyl iodide la: Ar is 4BTCGH4, R is H], 6-(4-fluorophenyl)hexyl iodide [Vla; Ar is EXAMPLE 1 3-Ethyl-6-(3,4-methylenedioxyphenyl)-3-hexenyl dl-2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylate [1; R is 2,2-dimethyl-3-( Z-methyl- 1 -propenyl)cyclopropyl, Y is C(C H )=CHCH CH Ar is 3 ,4-methylenedioxyphenyl] To a solution of 7.05 g. of dl-chrysanthemic acid in 25 ml. of methanol was added a solution of 2.70 g. of potassium hydroxide (87%) in 75 ml. of methanol. The resulting solution was concentrated to dryness, and to the residue of potassium dl-chrysanthemate was added a solution of 15 g. of 3-ethyl-6-(3,4-methylenedioxyphenyl)-3-hexenyl iodide (Preparation D1) in 100 ml. of dimethylformamide. The reaction mixture was warmed at 45C. for 2 days and then concentrated to remove the organic solvents. The residue was partitioned between water and ether, and the ether layer was washed with dilute sodium hydroxide solution, dried over anhydrous magnesium sulfate and concentrated. The residue was chromatographed on a column of silica gel and the column eluted with pentane containing increasing amounts of benzene. Fractions obtained with benzenepentane 7:3 provided 9.6 g. of 3- ethyl-6-(3,4-methylenedioxyphenyl)3-hexenyl dl-2,2- dimethyl-3-( 2-methyl- 1 -propenyl )cyclopropanecarboxylate as a light yellow oil.

Anal. Calcd. for C i-1 0 C, 75.34; H, 8.60.

Found: C, 75.62; H, 8.73.

infrared (IR) (oil film) A "'2 3.455 +shldrs. (CH); 5.82s (C=O); 603w, 6.24wm, 6.67s, 6.74s, 6.95s (unsatn. CH).

Nuclear Magnetic Resonance (NMR) CDCl internal tetramethylsilane (TMS)]8 ppm (Ratio) 675(3) (arom); 595(2) O-CH O); 4.8-5.6(2) (=CH);4.15(2)(COOCH -);1.8-2.8(9)(CH X 4 CH-C=O); 0.7-1 .8( 16) (cyclopropyl) CH 5 Me).

3-Ethyl-6-(3,4-methylenedioxyphenyl)-3-hexenyl dl- 2,2-dimethyl-3-(2-methyl-l-propenyUcyclopropanecarboxylate was found to have minimum inhibitory concentrations in vitro against rhino-2, equine rhino and respiratory syncitial virus of 0.6, 6 and 12 micrograms per milliliter, respectively.

EXAMPLE 2 3-Ethyl-6-( 3,4-methylenedioxyphenyl)-3-hexenyl acetate [1; R is CH Y is C(C H )=CHCH CH Ar is 3,4-methylenedioxyphenyl] A. mixture of 12.7 g. of 3-ethyl-6-(3,4- methylenedioxyphenyl)-3-hexenyl iodide (Preparation Di) and 3.5 g. of potassium acetate in 75 ml. of dimethylformamide was warmed at 45C. for about 16 hours. The reaction mixture was filtered and concentrated to remove the solvent. The residue was partitioned between water and ether, and the ether solution was concentrated. The residue was distilled at 127-l30C. (0.005 mm.) and then chromatographed on a column of silica gel. The column was eluted with pentane containing increasing amounts of benzene. Fractions obtained with benzene-pentane 6:4 provided g. of 3-ethyl-6-(3,4-methylenedioxyphenyl)-3- hexenyl acetate as an amber oil.

Anal. Calcd. for C H Op C, 70.32; H, 7.64.

Found; C. 70.19; H, 7.71.

IR (1/2% KBr) A if 3.45s shldrs. (CH); 5.79s (C4)); 6.25m 6.67mss, 6.74s, 6.95s (arom CH).

NMR (20% CDCl internal TMS) 8 ppm (Ratio) 673(3) (arom); 5.92(2) (OCH O); 5.22(1) (=CH)-,4.13(2)(C0OCH2-); 1.72.8(l1)(aliph.C1-1 CH;,-C=O-); 092(3) (Me triplet).

3-Ethyl-6-( 3,4-methylenedioxyphenyl)-3-hexenyl acetate was found to have a minimum inhibitory concentration in vitro against rhino-2 and para-influenza virus of 2.5 micrograms per milliliter.

3-Ethyl-6-(3,4-methylenedioxyphenyl)-3-hexenyl acetate was found to be pesticidal against dock beetle larvae at a concentration of 20 micrograms per insect.

EXAMPLE 3 3-Ethyl-6-(3,4-methylenedioxyphenyl)-3-hexenyl 3-methylcrotonate [1; R is (CH ),C=CH. Y is C(C2H5) (:HCH2cH2, AT is 3,4-methylenedioxyphenyl] A mixture of 17.9 g. of 3-ethyl-6-(3,4- methylenedioxyphenyl)-3-hexenyl iodide (Preparation D1) and 6.1 g. of sodium 3.3-dimethylacrylate in 150 ml. of dimethylformamide was heated at 52C. for 3 hours and then stirred at 40C. for 2% days. The reaction mixture was concentrated in vacuo and the residue partitioned between water and ether. The ether was dried over anhydrous magnesium sulfate, concentrated, and the residue (21 g.) chromatographed on silica gel. The chromatograph column was eluted with pentane containing increasing amounts of benzene. Fractions obtained with pentane-benzene 8:2 gave 6.2 g. of 3-ethyl-6-(3,4-methylenedioxyphenyl)-3-hexenyl 3-methylcrotonate as a light yellow oil.

Anal. Calcd. for czol'lzgofi C, 72-

Found: C, 72.71; H, 8.09.

IR (oil film) A "'3' 3.4Sms shldrs. (CH); 5.86s (conj. COOR); 6.09m (C=C); 6.25w, 6.68ms, 6.74s, 6.96s (arom CH). NMR (20% CDCl internal TMS) 8 ppm (Ratio) 674(3) (arom); 590(2) (OCH,O); 5.70. 5.22(2') (=CH X 2); 4.15(2') (COOCH 1.7-2.8(14') (Me -C=, CH 0.9(3-4) (Me triplet).

3-Ethyl-6-(3,4-methylenedioxyphenyl)-3-hexenyl 3- methylcrotonate was found to have minimum inhibitory concentrations in vitro against rhino-2, equine rhino and para-influenza virus of 3, l2 and 12 micrograms per milliliter, respectively.

3-Ethyl-6-(3,4-methylenedioxyphenyl)-3-hexenyl 3- methylcrotonate was found to have pesticidal activity when tested against yellow mealworm pupae (tenebrio) at a concentration of 100 micrograms per insect, against dock beetle larvae at 20 micrograms per insect, and against rhodnius prolixus nymph at 100 micrograms per insect.

EXAMPLE 4 3-Methyl-6-(3,4-methylenedioxyphenyl)-3-hexenyl formate [1; R is H, y is C(CH )=CHCH CH Ar is 3,4- methylenedioxyphenyl] is prepared by treating 3 methyl-6-(3,4-methylenedioxyphenyl)-3-hexenyl iodide (Preparation D3) and potassium formate according to the procedure of Example 2. The compound is obtained in the form of a light yellow mobile oil.

1R (oil film) It "'I." 3.45mms (CH); 5.82s (C=O); 6.25ws, 6.66ms, 6.73ms, 6.95ms (arom CH).

3-Methyl-6-( 3,4-methylenedioxyphenyl )-3-hexeny1 formate was found to have pesticidal activity when tested against dock beetle larvae at a concentration of 20 micrograms per insect. against rhodnius prolixus nymph at micrograms per insect, and against dock beetle eggs at 100 ppm.

EXAMPLE 5 3-Ethyl-6-(3,4-methylenedioxyphenyl)-3-hexenyl piperonylate [1; R and Ar are 3,4-methylenedioxyphenyl, Y is C(C H )=CHCH CH A mixture of 32.7 g. of 3-ethyl-6-(3,4- methylenedioxyphenyl)-3-hexenyl iodide (Preparation D1) and 18.8 g. of sodium piperonylate in 400 ml. of dimethylformamide was warmed at 50C. for about 16 hours. The product was isolated and chromatographed on a column of silica gel. The column was eluted with chloroform-ether 8:2 to give 19.95 g. of 3-ethyl-6(3,4- methylenedioxyphenyl)-3-hexenyl piperonylate as a light yellow oil.

Anal. Calcd. for C H O C, 69.88; H, 6.10.

Found: C, 69.50; H.619.

IR (oil film) A "'2 3.45s shldrs. (CH); 5.86: (conj. C=O-OR); 6.18m, 6.25mms, 6.67s, 6.67s, 6.74s, 6.95s (unsat. C=C, arom, CH).

NMR (20% CDCI internal TMS) 8 ppm (Ratio) 6.6-7.8(6) (arom); 6.02, 5.510(4) (OCH,--O X 2); 528(1) (=CH); 435(2) (COO-CH,); 1.83-2.77(8) (CH X 4); 095(3) (Me triplet).

3-Ethyl-6-( 3 ,4-methylenedioxyphenyl )-3 -hexeny1 piperonylate was found to have pseticidal activity when tested againt dock beetle larvae at a concentration of 20 micrograms per insect, against mosquito larvae at 6.6 ppm., and against salt marsh caterpillar eggs at 100 PP According to the methods of the preceding examples, 3-ethyl-6-(3,4-methylenedioxyphenyl)-3-hexenyl iodide (Preparation D1) can be caused to react with potassium cyclohexanecarboxylate, potassium cyclohex- 2-enecarboxylate, potassium undecanoate or potassium 3-cyclopentylpropionate to produce, respectively:

3-ethyl-6-(3,4-methylenedioxyphenyl-3-hexenyl cyclohexanecarboxylate [I; R is cyclohexyl, Y is C(C H )=CHCH,CH Ar is 3,4- methylenedioxyphenyl]; 3-ethyl-6-(3,4-methylenedioxyphenyl)3-hexenyl cyclohex-2-enecarboxylate [1; R' is cyclohex- 2-ene, Y is C(C,H )=CHCH,CH,. Ar is 3.4- methylenedioxyphenyl]; 3-ethyl-6-(3,4-methylenedioxyphenyl) 3-hexenyl unclecanoate [1; R is CH (CH,) Y is C(C2H5MHCH2CH2, A! 15 3,4- methylenedioxyphenyl]; or 3-ethyl-6-(3,4-methylenedioxyphenyl)-3-hexenyl 3-cyclopentylpropionate [1; R is cyclopentylCH,CH Y is C(C H )=CHCH,,CH Ar is 3,4-methylenedioxyphenyl].

According to the methods of the foregoing examples, the following iodide intermediates: 6-(3,4- methylenedioxyphenyl)-3-hexenyl iodide (Preparation .1.- 3-ethyl-6-(3,4-dimethoxyphenyl)-3-hexenyl iodir (Preparation D4); 6-(4-methoxyphenyl)-3- hexenyl iodide (Preparation D5); 6-(4-methoxyphenyl)hexyl iodide (Preparation D6); 6-(4- chlorophenyl)hexyl iodide (Preparation D7); 3-ethyl- 6-(4-carbomethoxyphenyl)-3-hexenyl iodide (Preparation D8); 3-ethyl-6-(3,4-methylenedioxyphenyl)-3,5-

hexadienyl iodide (Preparation D9); 3-isopropyl-6- (3 ,4-methylenedioxyphenyl )he xyl iodide; 3-butyl-6- (3,4-methylenedioxyphenyl )hexyl iodide; 6-( 3 ,4- dichlorophenyl )hexyl iodide; 6-( 2,4-

dichlorophenyl)hexyl iodide; 6-(4-bromophenyl)hexyl iodide; 6-(4-fluorophenyl)hexyl iodide; 6-(4- trifluoromethoxyphenyl)hexyl iodide; and 6-(4- trifluoromethylphenyl)hexyl iodide can be caused to react with potassium acetate to give. respectively:

6-(3.4-methylenedioxyphenyl)-3-hexenyl acetate [1;

R' is CH Y is CH=CHCH CH Ar is 3,4- methylenedioxyphenyl]; 3ethyl-6-(3,4-dimethoxyphenyl)-3-hexenyl acetate [1; R is CH;,, Y is C(C l-1 )#JHCH CH Ar is a )2 e al 6-(4-methoxyphenyl)-3-hexenyl acetate [1; R is CH Y is CH=CHCH CH Ar is 4-CH OC H 6-(4-methoxyphenyl)hexyl acetate [1; R is CH;,, Y is CH CH,CH CH Ar is 4CH;,OC H 6-(4-chlorophenyl)hexyl acetate [1; R is CH Y is CH CH CH CH Ar is 4ClC H 3-ethyl-6-(4-carbomethoxyphenyl)-3-hexenyl acetate [1; R is CH Y is C(C H )=CHCH CH Ar is 4CH O CC H,];

3-ethyl-6-( 3,4-methylenedioxyphenyl )-3,5-

hexadienyl acetate [1; R is CH Y is C(C H, )=CHCH=CH-, Ar is 3 ,4-

methylenedioxyphenyl]; 3-isopropyl-6-(3,4-methylenedioxyphenyl)hexyl acetate [1; R' is CH Y is C(iso-Pr)=CHCH Cl-1 Ar is 3,4-methylenedioxyphenyl]; 3-butyl-6-(3,4-methylenedioxyphenyl)hexyl acetate [1; R is CH Y is C(n-Bu)=CHCH- CH Ar is 3,4- methylenedioxyphenyl 6-(3,4-dichlorophenyl)hexyl acetate [1; R' is CH Y is CH CH CH CH Ar is 3,4-Cl C 1-1 6-(2,4-dichlorophenyl)hexyl acetate [1; R is CH Y is CH CH CH CH Ar is 2,4Cl C 1-l 6-(4-bromophenyl)hexyl acetate [1; R is CH;,, Y is CH CH CH Cl-h, Ar is 4BrC H 6-(4-fluorophenyl)hexyl acetate [1; R is CH Y is CH CH CH,CH Ar is 4FC l-1 6-(4-trifluoromethoxyphenyl)hexyl acetate [1; R' is CH Y is CH CH CH CH Ar is 4F COC l-[ and 6-(4-trifluoromethylphenyl)hexyl acetate [1; R is CH Y is cH cH,cH,cH Ar is 4F CC H,].

EXAMPLE 6 3 ,4-Epoxy3-ethyl-6-( 3 ,4-methylenedioxyphenyl )hexyl acetate.

To a solution of 9.47 g. (0.0326 mole) of 3-ethyl-6- (3,4-methylenedioxyphenyl)-3-hexenyl acetate (Example 2) in 50 ml. of anhydrous methylene dichloride was added a solution of 6.1 g. (0.033 mole) of mchloroperbenzoic acid in 150 ml. of anhydrous methylene dichloride over a period of 30 minutes with occasional cooling of the mixture in an ice bath. The reaction mixture was stirred for 2 hours at room temperature and then sodium bisulfite solution was added until the excess peracid had been destroyed (iodide test). The methylene dichloride solution was washed with 5% aqueous sodium carbonate and water, dried over anhydrous magnesium sulfate and concentrated in vacuo. The residue (9.4 g. of yellow oil) was combined with 5 g. of another run and chromatographed on a column of 280 g. of silica gel. The column was eluted with the pentane-benzene-ether solvent series. Fractions from benzene-ether 8:2 brought out the desired product,

10.5 g. of 3,4-epoxy-3-ethyl-6-(3,4-methylenedioxyphenyl)hexyl acetate as a light yellow oil.

Anal. Calcd. for C I-1 0 C, 66.65; H, 7.24.

Found: C, 66.35; H, 7.20.

1R (oil film) A "'11" 3.45ms shldrs. (CH); 5.79s (COOR); 6.26wm, 6.67ms, 6.74s, 6.96ms (arom CH).

3,4-Epoxy-3-ethyl-6-( 3 ,4-methylenedioxyphenyl)- hexyl acetate was found to have pesticidal activity when tested against dock beetle eggs at a concentration of ppm.

According to the foregoing procedure of Example 6, 3-ethyl-6-(3 ,4-methylenedioxyphenyl )-3-hexenyl piperonylate; 3-ethyl-6-( 3,4-methylenedioxyphenyl)-3- hexenyl cyclohexanecarboxylate; 3-ethyl-6-( 3 ,4- methylenedioxyphenyl)-3-hexenyl undecanoate; 3- ethyl-6-(3,4-methylenedioxyphenyl)-3-hexenyl 3-cyclopentylpropionate; 6-( 3 ,4-methylenedioxyphenyl)-3-hexenyl acetate; 3-ethyl-6-(3,4-dimethoxyphenyl)-3-hexenyl acetate; 6-(4-methoxyphenyl)-3- hexenyl acetate; or 3-ethyl-6-(4-carbomethoxyphenyl)-3-hexenyl acetate can be caused to react with m-chloroperbenzoic acid to give, respectively, 3.4- epoxy-3-ethyl-6-( 3,4-methylenedioxyphenyl )hexyl piperonylate; 3,4-epoxy-3-ethyl-6-(3,4-methylenedioxyphenyl)hexyl cyclohexanecarboxylate, 3,4-epoxy-3- ethyl-6-(3,4methylenedioxyphenyl)hexyl undecanoate; 3,4-epoxy-3-ethyl-6-(3,4-methylenedioxyphenyl)- hexyl 3-cyclopentylpropionate; 3.4-epoxy-6-(3,4- methylenedioxyphenyl)hexyl acetate; 3,4-epoxy-3- ethyl-6-(3,4-dimethoxyphenyl)hexyl acetate; 3,4- epoxy-6-(4-methoxypheny])hexyl acetate; or 3,4- epoxy-3-ethyl-6-( 4-carbomethoxyphenyl )hexyl acetate.

We claim: 1. A compound of the formula 0 It RC-O-CH CH Y-Ar wherein Y is selected from the group consisting of and R is hydrogen 3,4-methylenedioxyphenyl or a saturated or mono-olefinic hydrocarbon moiety having from i to 10 carbon atoms selected from the group consisting of alkyl, alkenyl, cycloalkyl, cycloalkenyl. alkylcycloalkyl, alkylcycloalkenyl and alkenylcycloalkyl,

R is hydrogen or lower-alkyl of 1 to 4 carbon atoms;

and

Ar is phenyl substituted by 3.4methylenedioxy or one or two monovalent substitutents selected from the group consisting of carbo-lower-alkoxy of 2 to acetate, according to claim 2.

5. 3-Ethyl-6-(3,4-methylenedioxyphenyl)-3-hexenyl 3-methylcr0tonate, according to claim 2.

6. 3-Methyl-6-(3,4-methylenedioxyphenyl)-3- 5 hexenyl formate, according to claim 2.

7. 3-Ethyl-6-(3,4-methylenedi0xyphenyl)-3-hexenyl piperonylate, according to claim 2. 

1. A COMPOUND OF THE FORMULA
 2. A compound according to claim 1 wherein Y is -C(R) CHCH2CH2- Ar is 3,4-methylenedioxyphenyl.
 3. 3-Ethyl-6-(3,4-methylenedioxyphenyl)-3-hexenyl dl-2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylate, according to claim
 2. 4. 3-Ethyl-6-(3,4-methylenedioxyphenyl)-3-hexenyl acetate, according to claim
 2. 5. 3-Ethyl-6-(3,4-methylenedioxyphenyl)-3-hexenyl 3-methylcrotonate, according to claim
 2. 6. 3-Methyl-6-(3,4-methylenedioxyphenyl)-3-hexenyl formate, according to claim
 2. 7. 3-Ethyl-6-(3,4-methylenedioxyphenyl)-3-hexenyl piperonylate, according to claim
 2. 